Luminescent Mononuclear and Binuclear ... - ACS Publications

Dec 29, 1999 - Shih-Sheng Sun, Jason A. Anspach, and Alistair J. Lees. Inorganic .... Peter Illner , Ralph Puchta , Frank W. Heinemann , Rudi van Eldi...
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Inorg. Chem. 2000, 39, 255-262

255

Luminescent Mononuclear and Binuclear Cyclometalated Palladium(II) Complexes of 6-Phenyl-2,2′-bipyridines: Spectroscopic and Structural Comparisons with Platinum(II) Analogues1,2 Siu-Wai Lai, Tsz-Chun Cheung, Michael C. W. Chan, Kung-Kai Cheung, Shie-Ming Peng,† and Chi-Ming Che* Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong ReceiVed September 13, 1999 The mononuclear cyclometalated Pd(II) complexes [Pd(L1)X] (HL1 ) 6-phenyl-2,2′-bipyridine; X ) Cl, 1a; Br, 1b; I, 1c), [Pd(L1)PPh3]+ (1d), [Pd(L2-5)Cl] [2a-5a, HL2-5 ) 4-(aryl)-6-phenyl-2,2′-bipyridine; aryl ) phenyl (2), 4-chlorophenyl (3), 4-tolyl (4), 4-methoxyphenyl (5)] and the binuclear derivatives [Pd2(L1-5)2(µ-dppm)]2+ (1e-5e, dppm ) bis(diphenylphosphino)methane) and [Pd2(L1)2(µ-dppC5)]2+, (1f, dppC5 ) 1,5-bis(diphenylphosphino)pentane) were prepared. The crystal structures of 1d(ClO4), 1e(ClO4)2‚DMF, and 2e(ClO4)2 have been determined by X-ray crystallography. The magnitude of the Pd-Pd distances in 1e and 2e (3.230(1) and 3.320(2) Å, respectively) suggest minimal metal-metal interaction, although π-stacking of the aromatic ligands (interplanar separations 3.34 and 3.35 Å, respectively) is evident. All complexes display low-energy UV absorptions at λ ∼ 390 nm, which are tentatively assigned to 1MLCT transitions; red shifts resulting from Pd-Pd interactions in the binuclear species are not apparent. The complexes in this work are non-emissive at 298 K, but the cationic derivatives exhibit intense luminescence at 77 K. The structured emissions of 1d and 1f in MeOH/EtOH glass (λmax 467-586 nm) and all cationic species in the solid state (λmax 493-578 nm) are assigned to intraligand excited states. Complexes 1e-5e display dual emissions in MeOH/EtOH glass at 77 K, and the broad structureless bands at λmax 626-658 nm are attributed to π-π excimeric IL transitions. A comparison between the photophysical properties of Pd(II) and Pt(II) congeners is presented.

Introduction The photophysics and photoreactivity of coordinatively unsaturated platinum(II) complexes3 and their applications as luminescent sensors4 are areas of considerable interest in inorganic photochemistry. Rich and diverse low-energy excited states, including IL (intraligand: π f π*), MLCT (metal-toligand charge transfer), [dσ* f pσ], and [dσ* f π*] (or MMLCT, metal-metal-to-ligand charge transfer), have been observed. Relatively scant attention has been focused upon the luminescent characteristics of palladium(II) complexes. Nevertheless, such investigations have been dominated by cyclometalated derivatives,5-7 and reports comparing Pd(II) and Pt(II) analogues can yield information on electronic structures and * Corresponding author. Fax: +852 2857 1586. Email: cmche@ hku.hk. † Department of Chemistry, National Taiwan University, Taipei, Taiwan. (1) Lai, S. W.; Chan, M. C. W.; Cheung, T. C.; Peng, S. M.; Che, C. M. Inorg. Chem. 1999, 38, 4046. (2) Cheung, T. C.; Cheung, K. K.; Peng, S. M.; Che, C. M. J. Chem. Soc., Dalton Trans. 1996, 1645. (3) For example, see: (a) Roundhill, D. M.; Gray H. B.; Che, C. M. Acc. Chem. Res. 1989, 22, 55. (b) Houlding, V. H.; Miskowski, V. M. Coord. Chem. ReV. 1991, 111, 145. (c) Kunkely, H.; Vogler, A. J. Am. Chem. Soc. 1990, 112, 5625. (d) Cummings, S. D.; Eisenberg, R. J. Am. Chem. Soc. 1996, 118, 1949. (e) Sandrini, D.; Maestri, M.; Balzani, V.; Chassot, L.; von Zelewsky, A. J. Am. Chem. Soc. 1987, 109, 7720. (4) For example, see: (a) Peyratout, C. S.; Aldridge, T. K.; Crites, D. K.; McMillin, D. R. Inorg. Chem. 1995, 34, 4484. (b) Kunugi, Y.; Mann, K. R.; Miller, L. L.; Exstrom, C. L. J. Am. Chem. Soc. 1998, 120, 589. (c) Wong, K. H.; Chan, M. C. W.; Che, C. M. Chem. Eur. J. 1999, 5, 2845. (5) Maestri, M.; Sandrini, D.; Balzani, V.; von Zelewsky, A.; Jolliet, P. HelV. Chim. Acta 1988, 71, 134.

excited states.8,9 The ability of cyclometalated Pd(II) complexes to undergo DNA cleavage has been described.10,11 We have previously studied various aspects of luminescent cyclometalated Pt(II) complexes bearing substituted 6-phenyl2,2′-bipyridine ligands.1,2,4c,12 As part of a continuing program dedicated to luminescent d8 systems, the preparation, crystal structures, and spectroscopic behavior of mono- and binuclear cyclometalated Pd(II) derivatives are presented. The correlation between Pd(II) and Pt(II) congeners has enabled evaluation of (6) (a) Schwarz, R.; Gliemann, G.; Jolliet, P.; von Zelewsky, A. Inorg. Chem. 1989, 28, 742. (b) Glasbeek, M.; Sitters, R.; van Veldhoven, E.; von Zelewsky, A.; Humbs, W.; Yersin, H. Inorg. Chem. 1998, 37, 5159. (7) Garcı´a-Herbosa, G.; Mun˜oz, A.; Maestri, M. J. Photochem. Photobiol. A: Chem. 1994, 83, 165. (8) (a) Maestri, M.; Sandrini, D.; Balzani, V.; von Zelewsky, A.; Cornioley-Deuschel, C.; Jolliet, P. HelV. Chim. Acta 1988, 71, 1053. (b) Barigelletti, F.; Sandrini, D.; Maestri, M.; Balzani, V.; von Zelewsky, A.; Chassot, L.; Jolliet, P.; Maeder, U. Inorg. Chem. 1988, 27, 3644. (c) Maestri, M.; Cornioley-Deuschel, C.; von Zelewsky, A. Coord. Chem. ReV. 1991, 111, 117. (d) Jolliet, P.; Gianini, M.; von Zelewsky, A.; Bernardinelli, G.; Stoeckli-Evans, H. Inorg. Chem. 1996, 35, 4883, and references therein. (9) Van Houten, K. A.; Heath, D. C.; Barringer, C. A.; Rheingold, A. L.; Pilato, R. S. Inorg. Chem. 1998, 37, 4647. (10) Newkome, G. R.; Onishi, M.; Puckett, W. E.; Deutsch, W. A. J. Am. Chem. Soc. 1980, 102, 4551. (11) (a) Suggs, J. W.; Dube, M. J.; Nichols, M. J. Chem. Soc., Chem Commun. 1993, 307. (b) Suggs, J. W.; Higgins, J. D., III; Wagner, R. W.; Millard, J. T. In Metal-DNA Chemistry, ACS Symposium Series 402; Tullius, T. D., Ed.; American Chemical Society: Washington DC, 1989; p 146. (12) (a) Tse, M. C.; Cheung, K. K.; Chan, M. C. W.; Che, C. M. Chem. Commun. 1998, 2295. (b) Lai, S. W.; Chan, M. C. W.; Cheung, K. K.; Che, C. M. Organometallics 1999, 18, 3327.

10.1021/ic991089g CCC: $19.00 © 2000 American Chemical Society Published on Web 12/29/1999

256 Inorganic Chemistry, Vol. 39, No. 2, 2000 metal-metal and ligand-ligand interactions in these systems and offered insight into their excited-state properties. Experimental Section General Procedures. K2PdCl4 (Strem), bis(diphenylphosphino)methane, and 1,5-bis(diphenylphosphino)pentane (dppm and dppC5, respectively; Aldrich) were used as received. 6-Phenyl-2,2′-bipyridine and its derivatives were prepared by literature methods.13 (Caution! perchlorate salts are potentially explosiVe and should be handled with care and in small amounts.) Details of solvent treatment for photophysical studies, instrumentation, and emission measurements have been provided previously.1 Syntheses. [Pd(L1-5)Cl] (1a-5a, HL1-5 ) 4-(aryl)-6-phenyl-2,2′bipyridine; aryl ) H (1), phenyl (2), 4-chlorophenyl (3), 4-tolyl (4), 4-methoxyphenyl (5)). A modification of Constable’s method was used.14 A mixture of K2PdCl4 (0.16 g, 0.49 mmol) and HL1-5 (except L3, 0.49 mmol) in CH3CN/H2O (15/15 mL) was refluxed for 18 h to give a yellow suspension, which was then evaporated to dryness. The product was extracted with dichloromethane, and the volume of extract was reduced to ∼5 mL. Addition of diethyl ether yielded a yellow solid, which was recrystallized by vapor diffusion of diethyl ether into an acetonitrile solution to afford a yellow crystalline solid. 1a. Yield: 0.16 g, 87%. Anal. Calcd for C16H11N2PdCl: C, 51.50; H, 2.97; N, 7.51. Found: C, 51.60; H, 2.85; N, 7.50. MS (+ve FAB): m/z 372 (M+), 337 (M+ - Cl). 1H NMR (DMSO-d6): δ 7.09 (m, 2H), 7.52 (d, 1H, J ) 7.1 Hz), 7.62 (d, 1H, J ) 7.2 Hz), 7.78 (m, 1H), 7.99 (d, 1H, J ) 7.9 Hz), 8.14 (t, 1H, J ) 7.9 Hz), 8.20 (d, 1H, J ) 7.9 Hz), 8.24 (t, 1H, J ) 7.8 Hz), 8.48 (d, 1H, J ) 8.0 Hz), 8.63 (d, 1H, J ) 4.7 Hz). 13C{1H} NMR (DMSO-d6): δ 119.7, 119.8, 123.1, 124.5, 124.7, 127.4, 129.6, 136.1, 140.1, 140.4, 148.0, 149.0, 153.5, 154.0, 155.1, 163.6. 2a. Yield: 0.19 g, 85%. Anal. Calcd for C22H15N2PdCl: C, 58.82; H, 3.37; N, 6.24. Found: C, 59.05; H, 3.25; N, 6.32. MS (+ve FAB): m/z 448 (M+). 1H NMR (CD3CN): δ 7.12 (m, 2H), 7.59-7.66 (m, 5H), 7.94 (m, 2H), 8.00 (m, 1H), 8.15 (m, 2H), 8.33 (d, 1H, J ) 7.9 Hz), 8.73 (m, 2H). 13C{1H} NMR (DMSO-d6): δ 117.9, 118.3, 124.4, 125.6, 125.9, 128.4, 128.5, 130.0, 130.5, 131.3, 137.0, 141.2, 149.0, 149.9, 152.0, 154.8, 155.0, 156.2, 164.7. 3a. A mixture of K2PdCl4 (0.16 g, 0.49 mmol) in H2O (10 mL) and HL3 (0.17 g, 0.50 mmol) in CH3CN (40 mL) was refluxed for 30 h to yield an orange suspension, which was filtered and washed with water (3 × 20 mL) and diethyl ether (3 × 20 mL). Extraction using dimethylformamide (DMF) and recrystallization by diffusion of diethyl ether into a DMF solution gave a yellow solid. Yield: 0.16 g, 67%. Anal. Calcd for C22H14N2PdCl2: C, 54.63; H, 2.92; N, 5.79. Found: C, 54.90; H, 3.10; N, 5.95. MS (+ve FAB): m/z 482 (M+). 1H NMR (DMSO-d6): δ 7.03-7.12 (m, 2H), 7.52 (br d, 1H, J ) 6.7 Hz), 7.68 (d, 2H, J ) 8.6 Hz), 7.76-7.84 (m, 2H), 8.16 (d, 2H, J ) 8.6 Hz), 8.24-8.31 (m, 2H), 8.54 (s, 1H), 8.63 (br d, 1H, J ) 4.3 Hz), 8.72 (d, 1H, J ) 8.0 Hz). 13C{1H} NMR (DMSO-d6): δ 116.9, 117.2, 123.5, 124.5, 125.0, 127.4, 129.0, 129.4, 129.6, 134.8, 135.3, 136.1, 140.2, 148.0, 149.0, 149.6, 153.9, 154.1, 155.2, 163.8. 4a. Yield: 0.17 g, 75%. Anal. Calcd for C23H17N2PdCl: C, 59.63; H, 3.70; N, 6.05. Found: C, 59.70; H, 3.85; N, 6.12. MS (+ve FAB): m/z 462 (M+). 1H NMR (DMSO-d6): δ 2.42 (s, 3H, Me), 7.09 (m, 2H), 7.42 (d, 2H, J ) 7.7 Hz), 7.53 (d, 1H, J ) 6.4 Hz), 7.79-7.86 (m, 2H), 8.04 (d, 2H, J ) 7.8 Hz), 8.30 (m, 2H), 8.53 (s, 1H), 8.65 (br d, 1H, J ) 4.2 Hz), 8.74 (d, 1H, J ) 7.6 Hz). 13C{1H} NMR (DMSOd6): δ 20.9 (Me), 116.6, 116.9, 123.4, 124.6, 124.8, 127.3, 127.4, 129.5, 129.7, 133.3, 136.2, 140.2, 140.3, 148.2, 149.1, 151.2, 153.9, 154.1, 155.5, 164.0. 5a. Yield 0.18 g, 77%. Anal. Calcd for C23H17N2OPdCl: C, 57.64; H, 3.58; N, 5.84. Found: C, 57.70; H, 3.65; N, 5.90. MS (+ve FAB): m/z 478 (M+). 1H NMR (DMSO-d6): δ 3.88 (s, 3H, OCH3), 7.047.17 (m, 4H), 7.52 (d, 1H, J ) 7.0 Hz), 7.76-7.86 (m, 2H), 8.13 (d, 2H, J ) 8.8 Hz), 8.28 (m, 2H), 8.51 (s, 1H), 8.62 (d, 1H, J ) 5.1 Hz), (13) Kro¨hnke, F. Synthesis 1976, 1. (14) Constable, E. C.; Henney, R. P. G.; Leese, T. A.; Tocher, D. A. J. Chem. Soc. Chem. Commun. 1990, 513.

Lai et al. 8.74 (d, 1H, J ) 8.0 Hz). 13C{1H} NMR (DMSO-d6): δ 55.4 (OCH3), 114.4, 115.9, 116.4, 123.4, 124.5, 124.9, 127.3, 128.0, 129.1, 129.4, 136.0, 140.2, 148.2, 148.9, 150.4, 153.7, 154.1, 155.3, 161.1, 163.6. [Pd(L1)Br], 1b. A mixture of 1a (0.20 g, 0.54 mmol) in CH3CN (30 mL) and excess NaBr (0.50 g, 4.86 mmol) in CH3OH (10 mL) was stirred for 24 h at room temperature to afford a yellow solid, which was filtered and washed with water and diethyl ether. Recrystallization by vapor diffusion of diethyl ether into a dimethylformamide solution afforded a yellow crystalline solid. Yield: 0.14 g, 63%. Anal. Calcd for C16H11N2PdBr: C, 46.02; H, 2.66; N, 6.71. Found: C, 46.10; H, 2.70; N, 6.70. MS (+ve FAB): m/z 417 (M+). 1H NMR (DMSO-d6): δ 7.01-7.11 (m, 2H), 7.63 (d, 1H, J ) 7.3 Hz), 7.73-7.79 (m, 2H), 8.00 (d, 1H, J ) 7.4 Hz), 8.13-8.27 (m, 3H), 8.48 (d, 1H, J ) 8.0 Hz), 8.78 (d, 1H, J ) 4.7 Hz). 13C{1H} NMR (DMSO-d6): δ 119.8, 119.9, 123.2, 124.6, 124.7, 127.5, 129.9, 138.4, 140.2, 140.3, 148.1, 149.9, 153.5, 153.9, 155.3, 163.4. [Pd(L1)I], 1c. The procedure for 1b was adopted using 1a (0.20 g, 0.54 mmol) and NaI (0.50 g, 3.34 mmol) to give the product as a yellow crystalline solid. Yield: 0.15 g, 62%. Anal. Calcd for C16H11N2PdI: C, 41.36; H, 2.39; N, 6.03. Found: C, 41.25; H, 2.27; N, 5.90. MS (+ve FAB): m/z 463 (M+). 1H NMR (DMSO-d6): δ 6.97 (t, 1H, J ) 7.1 Hz), 7.09 (t, 1H, J ) 6.9 Hz), 7.67 (d, 1H, J ) 6.9 Hz), 7.76 (t, 1H, J ) 6.0 Hz), 8.04 (d, 1H, J ) 6.9 Hz), 8.12 (d, 1H, J ) 7.8 Hz), 8.18-8.26 (m, 3H), 8.50 (d, 1H, J ) 8.0 Hz), 9.03 (d, 1H, J ) 4.8 Hz). 13C{1H} NMR (DMSO-d6): δ 119.9, 120.0, 123.4, 124.3, 125.0, 127.8, 130.4, 134.9, 140.1, 140.3, 148.4, 151.7, 153.4, 153.6, 155.5, 163.1. [Pd(L1)PPh3]ClO4, 1d(ClO4). A mixture of 1a (0.10 g, 0.27 mmol) and PPh3 (0.07 g, 0.27 mmol) in CH3CN/CH3OH (20/20 mL) was stirred for 3 h at room temperature. Excess LiClO4 (0.20 g, 1.63 mmol) was added to the resultant mixture, which was stirred at room temperature for 5 h and then filtered and concentrated to ∼5 mL. Addition of diethyl ether yielded a yellow solid, which was filtered and washed with diethyl ether. Recrystallization by vapor diffusion of diethyl ether into an acetonitrile solution gave a yellow crystalline solid. Yield: 0.15 g, 80%. Anal. Calcd for C34H26N2O4PdClP: C, 58.39; H, 3.75; N, 4.01. Found: C, 58.20; H, 3.70; N, 3.95. MS (+ve FAB): m/z 600 (M+). 1H NMR (DMSO-d ): δ 6.27 (d, 1H, J ) 5.2 Hz), 6.34 (m, 1H), 6.65 6 (t, 1H, J ) 7.3 Hz), 7.05-7.18 (m, 3H), 7.57-7.71 (m, 8H), 7.817.93 (m, 6H), 8.12-8.35 (m, 4H), 8.54 (d, 1H, J ) 8.0 Hz), 8.74 (br s, 1H). 13C{1H} NMR (DMSO-d6): δ 120.4, 120.6, 123.9, 125.9, 126.0, 126.4, 128.3, 128.7, 129.4, 129.9, 132.0, 134.9, 138.2, 138.3, 141.1, 142.4, 149.6, 149.8, 150.2, 152.8, 157.0, 162.2. 31P{1H} NMR (CD3CN): δ 40.38. [Pd2(L1-5)2(µ-dppm)](ClO4)2, 1e-5e(ClO4)2. A mixture of [PdL1-5Cl] (0.32 mmol) and dppm (0.16 mmol) in CH3CN/CH3OH (15/15 mL) was stirred for 12 h under a nitrogen atmosphere. Excess LiClO4 was added and the resulting solution was concentrated to ∼5 mL. Addition of diethyl ether afforded a yellow solid, which was filtered and washed with water (3 × 20 mL) and diethyl ether (2 × 20 mL). Recrystallization by vapor diffusion of diethyl ether into an acetonitrile solution afforded yellow crystals. 1e(ClO4)2. Yield: 0.16 g, 79%. Anal. Calcd for C57H44N4O8Pd2Cl2P2: C, 54.39; H, 3.52; N, 4.45. Found: C, 54.52; H, 3.38; N, 4.32. MS (+ve FAB): m/z 1157 (M+ + ClO4). 1H NMR (CD3CN): δ 4.60 (t, 2H, 2J(PH) ) 12.6 Hz, PCH2P), 6.02 (d, 2H, J ) 5.2 Hz), 6.28 (t, 2H, J ) 7.4 Hz), 6.48 (t, 2H, J ) 7.4 Hz), 6.68-6.75 (m, 4H), 6.98 (d, 2H, J ) 7.7 Hz), 7.39-7.47 (m, 10H), 7.55-7.59 (m, 4H), 7.757.98 (m, 16H). 13C{1H} NMR (CD3CN): δ 21.3 (t, 1J(PC) ) 22 Hz, PCH2P), 121.0, 124.1, 127.2, 127.8, 130.4, 131.1, 133.2, 134.5, 139.9, 140.9, 143.0, 150.0, 151.5, 152.3, 153.7, 157.1, 163.2. 31P{1H} NMR (CD3CN): δ 35.95. 2e(ClO4)2. Yield: 0.18 g, 78%. Anal. Calcd for C69H52N4O8Pd2Cl2P2: C, 58.74; H, 3.71; N, 3.97. Found: C, 58.50; H, 3.65; N, 3.92. MS (+ve FAB): m/z 1311 (M+ + ClO4). 1H NMR (CD3CN): δ 4.63 (t, 2H, 2J(PH) ) 12.7 Hz, PCH2P), 6.07 (d, 2H, J ) 5.2 Hz), 6.31 (t, 2H, J ) 7.2 Hz), 6.49 (t, 2H, J ) 7.5 Hz), 6.74-6.81 (m, 4H), 7.19 (d, 2H, J ) 7.1 Hz), 7.37-7.61 (m, 26 H), 7.86 (t, 4H, J ) 7.9 Hz), 7.94 (s, 2H), 8.12 (d, 6H, J ) 8.0 Hz). 13C{1H} NMR (CD3CN): δ 18.9 (t, 1J(PC) ) 22 Hz, PCH2P), 121.5, 124.6, 124.7, 125.1, 125.8,

d8-d8 and π-π Interactions in Pd(II) Luminophores

Inorganic Chemistry, Vol. 39, No. 2, 2000 257

Table 1. Crystal Data formula fw crystal system space group color crystal size, mm a, Å b, Å c, Å β, deg V, Å3 Z Dc, g cm-3 µ, cm-1 F(000) 2θmax, deg R,a Rwb residual F, e Å-3 a

1d(ClO4)

1e(ClO4)2‚DMF

2e(ClO4)2

C34H26N2O4PdClP 699.44 monoclinic P21/c yellow 0.15 × 0.25× 0.30 9.801(1) 20.122(1) 15.205(1) 98.096(9) 2968.5(5) 4 1.565 8.12 1416 50 0.040, 0.056 -0.42, +1.02

C57H44N4O8Pd2Cl2P2‚(CH3)2NCHO 1331.78 monoclinic P21/c yellow 0.05 × 0.25 × 0.25 15.602(2) 13.253(3) 27.213(3) 98.70(2) 5562(1) 4 1.590 8.64 2696 48 0.071, 0.087 -0.73, +1.18

C69H52N4O8Pd2Cl2P2 1410.83 monoclinic P21/c yellow 0.30 × 0.30 × 0.45 14.331(3) 14.535(3) 31.901(8) 93.55(4) 6632(3) 4 1.413 7.09 2849 45 0.065, 0.084 -1.12, +1.05

R ) ∑||Fo| - |Fc||/∑|Fo|. b Rw ) [∑w(|Fo| - |Fc|)2/∑w|Fo|2]1/2.

127.6, 128.5, 129.1, 129.5, 129.8, 130.5, 133.9, 137.2, 138.1, 147.3, 148.9, 149.6, 151.3, 151.8, 154.4, 160.7. 31P{1H} NMR (CD3CN): δ 36.66. 3e(ClO4)2. Yield: 0.15 g, 65%. Anal. Calcd for C69H50N4O8Pd2Cl4P2: C, 56.01; H, 3.41; N, 3.79. Found: C, 55.88; H, 3.28; N, 3.65. MS (+ve FAB): m/z 1380 (M+ + ClO4). 1H NMR (CD3CN): δ 4.61 (t, 2H, 2J(PH) ) 12.7 Hz, PCH2P), 6.02 (m, 2H), 6.28 (m, 2H), 6.40 (t, 2H, J ) 7.4 Hz), 6.79 (m, 4H), 7.21 (d, 2H, J ) 7.6 Hz), 7.338.22 (m, 36H). 13C{1H} NMR (CD3CN): δ 21.2 (t, 1J(PC) ) 22 Hz, PCH2P), 116.7, 123.3, 126.3, 126.5, 126.9, 129.0, 129.3, 129.4, 130.4, 130.9, 131.2, 131.6, 132.3, 134.0, 136.8, 138.9, 139.8, 148.9, 150.4, 151.3, 152.0, 153.1, 156.2, 162.6. 31P{1H} NMR (CD3CN): δ 36.64. 4e(ClO4)2. Yield: 0.16 g, 70%. Anal. Calcd for C71H56N4O8Pd2Cl2P2: C, 59.26; H, 3.92; N, 3.89. Found: C, 59.20; H, 3.85; N, 3.73. MS (+ve FAB): 1339 (M+ + ClO4). 1H NMR (CD3CN): δ 2.42 (s, 6H, Me), 4.61 (t, 2H, 2J(PH) ) 12.7 Hz, PCH2P), 6.04 (d, 2H, J ) 5.0 Hz), 6.30 (t, 2H, J ) 6.9 Hz), 6.45 (t, 2H, J ) 7.3 Hz), 6.73-6.80 (m, 4H), 7.18 (d, 6H, J ) 7.8 Hz), 7.47-7.55 (m, 20H), 7.82-7.91 (m, 6H), 8.10 (d, 6H, J ) 8.0 Hz). 13C{1H} NMR (CD3CN): δ 20.6 (Me), 20.9 (t, 1J(PC) ) 22 Hz, PCH2P), 116.4, 123.2, 126.2, 126.4, 126.8, 127.3, 129.4, 129.8, 130.1, 131.0, 131.3, 131.6, 132.2, 132.4, 138.8, 139.7, 141.4, 149.0, 150.5, 151.2, 152.9, 153.1, 156.2, 162.3. 31P{1H} NMR (CD3CN): δ 36.53. 5e(ClO4)2. Yield: 0.17 g, 73%. Anal. Calcd for C71H56N4O10Pd2Cl2P2: C, 57.98; H, 3.84; N, 3.81. Found: C, 57.85; H, 3.75; N, 3.90. MS (+ve FAB): m/z 1369 (M+ + ClO4). 1H NMR (CD3CN): δ 3.88 (s, 6H, OMe), 4.59 (t, 2H, 2J(PH) ) 12.7 Hz, PCH2P), 6.04 (d, 2H, J ) 5.2 Hz), 6.28 (t, 2H, J ) 7.6 Hz), 6.43 (t, 2H, J ) 7.4 Hz), 6.736.80 (m, 4H), 6.87 (d, 4H, J ) 8.8 Hz), 7.18 (d, 2H, J ) 7.7 Hz), 7.46-7.60 (m, 20H), 7.78-7.89 (m, 6H), 8.11 (m, 6H). 13C{1H} NMR (CD3CN): δ 22.1 (t, 1J(PC) ) 22 Hz, PCH2P), 56.3 (OMe), 115.6, 117.0, 117.7, 124.1, 127.1, 127.3, 127.8, 128.5, 130.0, 130.4, 131.1, 139.8, 140.7, 150.2, 151.5, 152.3, 153.9, 157.4, 163.0, 163.3. 31P{1H} NMR (CD3CN): δ 36.29. [Pd2(L1)2(µ-dppC5)](ClO4)2, 1f(ClO4)2. The procedure for 1e was adopted using 1a (0.15 g, 0.40 mmol) and 1,5-bis(diphenylphosphino)pentane (0.09 g, 0.20 mmol) to yield a yellow crystalline solid. Yield: 0.19 g, 72%. Anal. Calcd for C61H52N4O8Pd2Cl2P2: C, 55.72; H, 3.99; N, 4.26. Found: C, 55.68; H, 3.92; N, 4.20. MS (+ve FAB): m/z 1215 (M+ + ClO4). 1H NMR (DMSO-d6): δ 1.74; 1.83; 2.70 (br m, 10H, P(CH2)5P), 6.45 (m, 2H), 6.67 (m, 4H), 6.97 (t, 2H, J ) 7.5 Hz), 7.14 (t, 2H, J ) 7.0 Hz), 7.46 (m, 8H), 7.55 (m, 4H), 7.67 (d, 2H, J ) 7.2 Hz), 7.76 (m, 8H), 8.06 (m, 4H), 8.19-8.24 (m, 4H), 8.41 (d, 2H, J ) 8.0 Hz). 13C{1H} NMR (DMSO-d6): δ 22.6 (d, J(PC) ) 30 Hz, PCH2), 24.3 (d, J(PC) ) 4 Hz, PCH2CH2), 30.3 (t, J(PC) ) 16 Hz, P(CH2)2CH2), 119.2, 119.3, 122.7, 124.8, 125.6, 128.1, 128.7, 129.1, 129.2, 130.5, 132.0, 136.0, 136.1, 139.9, 141.1, 148.2, 149.5, 149.6, 151.6, 155.6, 160.9. 31P{1H} NMR (CD3CN): δ 31.51.

X-ray Crystallography. Crystals of 1d(ClO4), 1e(ClO4)2‚DMF, and 2e(ClO4)2 were obtained by vapor diffusion of diethyl ether into acetonitrile/dimethylformamide (DMF) solutions. Crystal data and details of collection and refinement are summarized in Table 1. The following data are listed in the order 1d(ClO4)/1e(ClO4)2‚DMF. A total of 5408/9147 unique reflections was collected at 301 K on a Rigaku/ Nonius diffractometer [λ(Mo-KR) ) 0.7107 Å, ω-2θ scans]. The structures were solved by Patterson methods, expanded using Fourier techniques (PATTY15), and refined by full-matrix least squares using the TeXsan16 software package for 4180/5692 absorption-corrected (transmission 0.88-1.00/0.83-1.00) reflections with I > 3σ(I) and 388/ 689 parameters. For 2e(ClO4)2, a total of 8647 unique reflections was collected at 298 K on a Nonius diffractometer [λ(Mo-KR) ) 0.7107 Å, θ/2θ scans]. The structure was solved by Patterson methods, expanded using Fourier techniques, and refined by least-squares treatment on F2 using the NRCVAX program for 4698 absorptioncorrected (transmission 0.65-1.00) reflections with I > 2σ(I) and 793 parameters. The pairs of atoms N(1)/C(1) for 1d(ClO4), N(1)/C(1) and N(3)/C(17) for 1e(ClO4)2‚DMF, and N(1)/C(22) and N(3)/C(44) for 2e(ClO4)2 were differentiated by their temperature factors; interchanging the respective C and N atoms resulted in unreasonable temperature factors and/or higher R values.

Results and Discussion Synthesis and Characterization. The complexes described in this study are illustrated in Figure 1. Cyclopalladation of the ligands HL1-5, prepared by Kro¨hnke syntheses,13 is accomplished by modifying the procedure described by Constable and co-workers.14 The various 4-aryl substituents in HL1-5 may be expected to impose different electronic demands upon the palladium center. Hence complexes 1a-5a are synthesized by interaction of K2PdCl4 with HL1-5 respectively at elevated temperatures in an acetonitrile/water mixture. The coordinated chloride auxiliary in this series allows derivatization of the [Pd(L1-5)] moieties through ligand-substitution reactions. The neutral complexes [Pd(L1)X] (X ) Br, 1b; I, 1c) and the cationic derivative [Pd(L1)PPh3]+ (1d) are formed by reaction of 1a with NaX and triphenylphosphine respectively at room temperature. The binuclear cyclometalated Pd(II) complexes 1e-5e and 1f are conveniently prepared by treatment of the respective (15) PATTY: Beurskens, P. T.; Admiraal, G.; Beursken, G.; Bosman, W. P.; Garcia-Granda, S.; Gould, R. O.; Smits, J. M. M.; Smykalla, C. The DIRDIF program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands, 1992. (16) TeXsan: Crystal Structure Analysis Package; Molecular Structure Corporation: The Woodlands, TX, 1985 and 1992.

258 Inorganic Chemistry, Vol. 39, No. 2, 2000

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Figure 2. Perspective view of [Pd(L1)PPh3]+, 1d (50% probability ellipsoids). Table 2. Selected Bond Lengths (Å) and Angles (deg)

Figure 1. Nomenclature for ligands and complexes.

mononuclear precursor with the appropriate diphosphine ligand. In the 1H NMR spectra, the methylene group of the dppm bridge appears as a distinctive triplet resonance at ca. 4.6 ppm (2J(PH) ) 12.7 Hz). The positive FAB mass spectra for 1e-5e contain a prominent signal corresponding to the (M+ + ClO4) fragment rather than the molecular cation M+. Crystal Structures: Pd-Pd and π-π Separations. A number of palladium(II) complexes have been crystallographically characterized during this investigation. Comparisons with the structures of platinum(II) congeners can provide insight into the extent of metal-metal and ligand-ligand interactions in these systems. Selected bond distances and angles for 1d(ClO4), 1e(ClO4)2‚DMF, and 2e(ClO4)2 are listed in Table 2. Constable and co-workers14 have communicated the crystal structure of 1a. The Pd atom in the cation 1d (Figure 2) resides in a highly distorted square planar environment. The bite angle of 157.6(2)° exhibited by L1 is typical for cyclometalating 6-phenyl-2,2′-bipyridine ligands. The palladium-ligand distances are comparable to those in the platinum analogue2 (e.g., Pd-P, 2.273(1) Å; Pt-P, 2.243(3) Å). In the crystal lattice of 1d, distinct π-π stacking interactions are not apparent due to poor overlap of L1 ligands, although some close intermolecular contacts (3.5-3.7 Å) are observed. This is in contrast to the structure of [Pt(L1)PPh3]ClO4,2 which displays head-to-tail π-stacking interactions with intermolecular plane separations of 3.35 Å. In addition, Jeffrey, Ward, and co-workers17 have reported the crystal structure of the Pd(II) complex [Pd(L′)Cl] (HL′ ) 6-(2-hydroxyphenyl)-2,2′-bipyridine), which reveals an average stacking distance of 3.44 Å between the L′ planes. Like the platinum equivalent [Pt2(L1)2(µ-dppm)]2+,2 the molecular structures of the cations [Pd2(L1)2(µ-dppm)]2+ (1e) (17) Bardwell, D. A.; Crossley, J. G.; Jeffery, J. C.; Orpen, A. G.; Psillakis, E.; Tilley, E. E. M.; Ward, M. D. Polyhedron, 1994, 13, 2291.

Pd(1)-P(1) Pd(1)-N(1) P(1)-Pd(1)-N(1) P(1)-Pd(1)-N(2)

[Pd(L1)PPh3]ClO4, 1d(ClO4) 2.273(1) Pd(1)-N(2) 2.191(4) Pd(1)-C(1) 106.7(1) P(1)-Pd(1)-C(1) 172.8(1) N(1)-Pd(1)-C(1)

2.020(4) 2.039(5) 95.6(1) 157.6(2)

[Pd2(L1)2(µ-dppm)](ClO4)2‚DMF, 1e(ClO4)2‚DMF Pd(1)-P(1) 2.266(2) Pd(2)-P(2) 2.272(2) Pd(1)-N(1) 2.116(9) Pd(2)-N(3) 2.17(1) Pd(1)-N(2) 2.025(8) Pd(2)-N(4) 2.055(8) Pd(1)-C(1) 2.17(1) Pd(2)-C(17) 2.07(1) P(1)-C(45) 1.845(9) P(2)-C(45) 1.829(9) P(1)-Pd(1)-N(1) 102.6(3) P(2)-Pd(2)-N(3) 105.6(3) P(1)-Pd(1)-N(2) 174.9(3) P(2)-Pd(2)-N(4) 174.9(2) P(1)-Pd(1)-C(1) 97.4(3) P(2)-Pd(2)-C(17) 97.4(3) N(1)-Pd(1)-C(1) 160.0(4) N(3)-Pd(2)-C(17) 156.9(4) Pd(1)-P(1)-C(45) 115.5(3) Pd(2)-P(2)-C(45) 115.9(3) P(1)-C(45)-P(2) 122.8(5) [Pd2(L2)2(µ-dppm)](ClO4)2, 2e(ClO4)2 Pd(1)-P(1) 2.279(5) Pd(2)-P(2) Pd(1)-N(1) 2.182(13) Pd(2)-N(3) Pd(1)-N(2) 2.003(12) Pd(2)-N(4) Pd(1)-C(22) 2.021(16) Pd(2)-C(44) P(1)-C(45) 1.853(17) P(2)-C(45) P(1)-Pd(1)-N(1) 105.2(4) P(2)-Pd(2)-N(3) P(1)-Pd(1)-N(2) 175.6(4) P(2)-Pd(2)-N(4) P(1)-Pd(1)-C(22) 96.8(5) P(2)-Pd(2)-C(44) N(1)-Pd(1)-C(22) 157.6(6) N(3)-Pd(2)-C(44) Pd(1)-P(1)-C(45) 116.1(5) Pd(2)-P(2)-C(45) P(1)-C(45)-P(2) 120.5(9)

2.280(5) 2.177(13) 1.991(13) 1.999(17) 1.856(17) 106.7(4) 175.7(4) 95.2(5) 157.0(6) 117.1(5)

and [Pd2(L2)2(µ-dppm)]2+ (2e) (Figures 3 and 4 respectively) depict two [Pd(Ln)] moieties tethered by a dppm linker. The intramolecular Pd-Pd separations of 3.230(1) Å in 1e and 3.320(2) Å in 2e are significantly greater than that expected for a strong Pd-Pd bonding interaction (typically 2.6-2.8 Å).18 Outside this range, longer Pd-Pd distances have been observed in [Pd2(µNS,η2-L)2Cl2(PMe3)2] (L ) heterocyclic 2-thiolate, 2.915(1)-3.104(2) Å),19 [Pd2(C6H4N(H)NdC(CH3)C5H4N)2(µ(18) For example, see: (a) Cotton, F. A.; Matusz, M.; Poli, R.; Feng, X. J. Am. Chem. Soc. 1988, 110, 1144. (b) Ogoshi, S.; Tsutsumi, K.; Ooi, M.; Kurosawa, H. J. Am. Chem. Soc. 1995, 117, 10415. (c) Tanase, T.; Ukaji, H.; Yamamoto, Y. J. Chem. Soc., Dalton Trans. 1996, 3059.

d8-d8 and π-π Interactions in Pd(II) Luminophores

Figure 3. Perspective view of [Pd2(L1)2(µ-dppm)]2+, 1e (35% probability ellipsoids).

Figure 4. Perspective view of [Pd2(L2)2(µ-dppm)]2+, 2e (30% probability ellipsoids).

dppm)](BF4)2 (3.114(1) Å),20 [Pd2(2-(5′-MeC6H3)-1,10-phen)2(µ-N-3,N-9-adenine)](NO3) (3.162(3) Å),11a and [Pd2(dppm)2(CN)4] (3.276(1) Å).21 The intermolecular Pd-Pd contact of 3.354(4) Å in [Pd(bpy)(CN)2]22 and the Pt-Pt distance of 3.270(1) Å in [Pt2(L1)2(µ-dppm)](ClO4)22 should also be noted. Since the latter is indicative of weak intermetal communication and the ionic radius of Pt(II) is larger than that for Pd(II), comparable intramolecular metal-metal separations in 1e, 2e, and [Pt2(L1)2(µ-dppm)]2+ imply that the degree of ground-state metal-metal interaction is even smaller in the Pd system. The small dihedral angles between the two [Pd(Ln)] mean planes in 1e and 2e (5.7 and 4.8° respectively) demonstrate that the intramolecular [Pd(Ln)] units are nearly coplanar. The average interplanar separation between the Ln ligands in 1e and 2e are 3.34 and 3.35 Å, respectively. This feature and the small (19) Yap, G. P. A.; Jensen, C. M. Inorg. Chem. 1992, 31, 4823. (20) Garcı´a-Herbosa, G.; Mun˜oz, A.; Miguel, D.; Garcı´a-Granda, S. Organometallics 1994, 13, 1775. (21) Yip, H. K.; Lai, T. F.; Che, C. M. J. Chem. Soc., Dalton Trans. 1991, 1639. (22) Che, C. M.; He, L. Y.; Poon, C. K.; Mak, T. C. W. Inorg. Chem. 1989, 28, 3081.

Inorganic Chemistry, Vol. 39, No. 2, 2000 259 dihedral angle signify π-stacking interactions within the binuclear complexes, even though there is apparently minimal Pd-Pd communication in the ground state. The torsion angle of 25.8° (defined by N(2)-Pd(1)-Pd(2)-N(4)) between the two [Pd(L1)] moieties in 1e is smaller than the corresponding angle of 44.6° in [Pt2(L1)2(µ-dppm)](ClO4)2.1,2 The magnitude of the latter was attributed to optimized π-π interactions between the aromatic ligands L1, to avoid repulsive forces arising from eclipsed overlap of π orbitals (i.e. torsion angle ca. 0°).23 Hence it appears that, like the metal-metal interaction, the π-π orbital overlap in 1e is inferior compared to the platinum analogue. The torsion angle between the two [Pd(L2)] moieties in 2e is 5.4° (defined by N(2)-Pd(1)-Pd(2)-N(4)). There are no close intermolecular contacts between the aromatic ligands in the crystal lattices of 1e and 2e (distance > 4 Å). Absorption Spectra. The UV-visible absorption spectra of the mono- and binuclear Pd(II) complexes depicted in this work have been obtained. The UV-vis spectral data of 1a-5a and 1b-1d in dichloromethane are listed in Table 3. For example, the absorption spectrum of 1a is shown in Figure 5. The intense absorptions at λmax ) 272, 278, 309, and 326 nm ( ∼ 104 dm3 mol-1 cm-1) are assigned to intraligand transitions of the cyclometalated ligand, based on similarities with the absorptions of the free ligand HL1. There is a moderately intense low-energy band tailing from λmax ) 360-450 nm with a shoulder at λ ∼ 390 nm. The  value at 390 nm is 1150 dm3 mol-1 cm-1 and we tentatively assign this band to a spin-allowed 4d(Pd) f π*(L1) (1MLCT) transition. Absorption bands at λmax ) 349-400 nm in the related complexes [Pd(C,N)2] (HC,N ) 2-phenylpyridine, 2-(2′-thienyl)pyridine, 7,8-benzoquinoline) have also been ascribed to MLCT transitions,5 and the red shift of similar bands in analogous Pt(II) derivatives provides support for this assignment (see below). The MLCT transition of the cationic derivative [Pd(terpy)Cl][PF6] was previously assigned at λmax ) 328-362 nm.24 Ligand-field d-d transitions have been invoked for absorptions in the 380-400 nm range for orthometalated azobenzene Pd(II) complexes,25 but unreasonably high  values (ca. 8 × 103 dm3 mol-1 cm-1) are reported. We reason that the  value at 390 nm for 1a is also larger than would be expected for d-d transitions in Pd(II) derivatives. Similar assignments can be made for complexes 1b, 1c, and 2a-5a: the absorptions at λmax e 370 nm are assigned as intraligand in nature while the low-energy bands at λmax g 390 nm are attributed to MLCT transitions. The low-energy absorption for 1d is blue-shifted to λmax 375 nm ( ) 1950 dm3 mol-1 cm-1) in CH3CN, and this is consistent with the expected increase in the energy of the MLCT transition for cationic species. The UV-visible spectral data of complexes 1e-5e and 1f in acetonitrile are listed in Table 4. The absorption spectrum of [Pd2(L1)2(µ-dppm)]2+ (1e) shows intense intraligand transitions at λmax 309 and 331 nm ( ∼ 104 dm3 mol-1 cm-1) and moderately intense and broad absorptions at λmax 378-401 nm ( ) 4900-3400 dm3 mol-1cm-1) (Figure 6). All the absorption bands obey Beer’s law in the concentration range 5 × 10-6 to 5 × 10-3 mol dm-3. By comparison with the mononuclear counterpart 1d, it is evident that the spectra are very similar, except that the  values are greater for 1e (Figure 6). This may be rationalized by an increase in the number of Pd(L1) chromophores per molecule. For d8 systems, a dσ* f π* metal(23) Hunter, C. A.; Sanders, J. K. M. J. Am. Chem. Soc. 1990, 112, 5525. (24) Zhang, W.; Bensimon, C.; Crutchley, R. J. Inorg. Chem. 1993, 32, 5808. (25) Wakatsuki, Y.; Yamazaki, H.; Grutsch, P. A.; Santhanam, M.; Kutal, C. J. Am. Chem. Soc. 1985, 107, 8153.

260 Inorganic Chemistry, Vol. 39, No. 2, 2000

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Table 3. UV-Visible Spectral Data of Mononuclear Complexesa λmax/nm (/dm3 mol-1cm-1)

complex Pd(L1

)Cl, 1a Pd(L2)Cl, 2a Pd(L3)Cl, 3a Pd(L4)Cl, 4a Pd(L5)Cl, 5a Pd(L1)Br, 1b Pd(L1)I, 1c [Pd(L1)PPh3](ClO4), 1d(ClO4)b a

272 (27 300), 278 (27 600), 309 (15 900), 326 (15 900), 342 (sh, 9500), 390 (sh, 1150), 421 (sh, 350) 263 (26 700), 287 (40 600), 328 (18 600), 349 (sh, 11 500), 394 (sh, 1600), 422 (sh, 510) 266 (25 400), 291 (39 900), 329 (18 600), 350 (sh, 12 000), 401 (sh, 1350), 428 (sh, 370) 263 (23 000), 294 (33 400), 329 (18 800), 346 (sh, 13 000), 369 (sh, 5100), 397 (sh, 1500), 422 (450) 262 (26 700), 278 (26 300), 312 (34 500), 335 (sh, 25 100), 347 (sh, 20 100), 369 (sh, 11 400), 398 (sh, 2350), 423 (540) 272 (22 300), 279 (23 000), 311 (15 300), 326 (14 700), 343 (sh, 9000), 395 (sh, 1100), 418 (sh, 410) 249 (28 500), 268 (22 000), 317 (15 800), 328 (15 000), 390 (sh, 2200), 418 (sh, 940) 243 (48 300), 267 (sh, 26 400), 306 (13 000), 331 (sh, 10 400), 375 (1950), 397 (sh, 1250)

In CH2Cl2 unless stated otherwise. b In acetonitrile.

Table 4. UV-Visible Spectral Data of Binuclear Complexes in Acetonitrile Complex

λmax/nm (/dm3 mol-1cm-1)

[Pd2(L1)2(µ-dppm)](ClO4)2, 1e(ClO4)2 [Pd2(L2)2(µ-dppm)](ClO4)2, 2e(ClO4)2 [Pd2(L3)2(µ-dppm)](ClO4)2, 3e(ClO4)2 [Pd2(L4)2(µ-dppm)](ClO4)2, 4e(ClO4)2 [Pd2(L5)2(µ-dppm)](ClO4)2, 5e(ClO4)2 [Pd2(L1)2(µ-dppC5)](ClO4)2, 1f(ClO4)2

309 (22 000), 331 (sh, 18 500), 378 (4900), 401 (sh, 3400) 286 (69 800), 311 (sh, 44 400), 386 (4900), 408 (sh, 3200) 288 (71 300), 314 (sh, 51 100), 390 (4800), 412 (sh, 3100) 291 (57 400), 316 (49 500), 387 (4700), 410 (sh, 2700) 303 (46 200), 330 (51 300), 396 (sh, 7100), 418 (sh, 2900) 307 (25 600), 318 (25 100), 378 (4700), 398 (sh, 3100)

Figure 7. Schematic molecular orbital diagram illustrating metalmetal and ligand-ligand interactions in binuclear polypyridine d8-d8 complexes. Figure 5. UV-vis absorption spectrum of 1a in CH2Cl2 at 298 K.

Figure 6. UV-vis absorption spectra of 1d and 1e in CH3CN at 298 K.

metal-to-ligand charge transfer (MMLCT) transition which is red-shifted from the MLCT transition of mononuclear species is expected for binuclear derivatives exhibiting significant metal-metal interaction (Figure 7).1,26 The virtual match (26) Miskowski, V. M.; Houlding, V. H. Inorg. Chem. 1991, 30, 4446.

between the low-energy absorptions at λ > 360 nm for 1d and 1e, together with the structural parameters (see above), thus imply very weak or minimal Pd-Pd interaction in 1e. Accordingly, the absorptions at λmax ) 378-401 nm for 1e are tentatively assigned as MLCT in nature like for 1d. Furthermore, the low-energy absorption of 1f, in which [Pd(L1)] units are separated by a long diphosphine ligand and Pd-Pd communication is disfavored, is almost identical to that for 1e (Table 4). This observation reinforces the notion that there is minimal ground-state metal-metal interaction in these binuclear Pd(II) complexes. Similar assignments can be made with respect to the absorption spectra of 2e-5e. Emission Spectra. All complexes in this account are nonemissive at room temperature. At 77 K, the cationic derivatives bearing phosphine ligands generally display more intense emissions than neutral species (Table 5). Indeed, the [Pd(L1-5)Cl] (1a-5a) and [Pd(L1)X] (X ) Br, 1b; I, 1c) solids are nonemissive at 298 and 77 K.27 The cationic complex [Pd(L1)(PPh3)]+ (1d) and the related dication [Pd2(L1)2(µ-dppC5)]2+ (1f) display vibronically structured emissions at λmax ) 467-576 and 474-586 nm, respectively, in 77 K glassy MeOH/EtOH solutions, with vibronic progressions of ca. 1300 cm-1 (Figure 8) and lifetimes (τ) in the order of 10-4 s. These highenergy bands can be assigned to intraligand (3IL) emission by the cyclometalated ligand L1. The cationic derivatives 1e(27) These complexes are weakly emissive in frozen dichloromethane at 77 K.

d8-d8 and π-π Interactions in Pd(II) Luminophores

Inorganic Chemistry, Vol. 39, No. 2, 2000 261

Table 5. 77 K Emission Data (complex concentration 1 × 10-4 M) λmax/nm complex

MeOH/EtOH (1:1)

Solid

[Pd2(L1)2(µ-dppm)](ClO4)2, 1e(ClO4)2 [Pd2(L2)2(µ-dppm)](ClO4)2, 2e(ClO4)2 [Pd2(L3)2(µ-dppm)](ClO4)2, 3e(ClO4)2 [Pd2(L4)2(µ-dppm)](ClO4)2, 4e(ClO4)2 [Pd2(L5)2(µ-dppm)](ClO4)2, 5e(ClO4)2 [Pd2(L1)2(µ-dppC5)](ClO4)2, 1f(ClO4)2 [Pd(L1)PPh3](ClO4), 1d(ClO4)

480, 510, 626 480, 523, 633 480, 523, 658 478, 514, 632 479 (sh), 517, 634 474 (max), 507, 542, 586 (sh) 467 (max), 501, 532, 576 (sh)

526, 553 516 (max), 556 529, 566 544 (max), 578 526 (max), 560 498 (max), 527 493 (max), 527, 563

Figure 8. Normalized 77 K emission spectra of 1d, 1e, and 1f in 1:1 MeOH/EtOH glass (λex ) 350 nm, * denotes instrumental artifact).

5e(ClO4)2, 1d(ClO4), and 1f(ClO4)2 are luminescent in the solid state at 77 K.28 Except for 1e(ClO4)2 and 3e(ClO4)2, highly structured emissions at λmax ) 493-578 nm are displayed, and these are ascribed to metal-perturbed 3IL excited states. The solid emissions of 1e(ClO4)2 (λmax ) 526-553 nm) and 3e(ClO4)2 (λmax ) 529-566 nm) are more diffuse. Complexes 1e-5e are luminescent in glassy MeOH/EtOH solutions (Table 5). The emission spectrum of 1e (Figure 8) shows sharp bands at λmax ) 480 and 510 nm (τ ) 160 µs, vibronic progression 1225 cm-1) and a broad structureless band at 626 nm (τ ) 90 µs). The high-energy structure resembles the intraligand emission of 1d and 1f and is therefore assigned to a 3IL excited state. The broad emission at 626 nm is tentatively assigned to an excimeric 3IL transition resulting from π-π interactions.29 There are evidently various static conformations for 1e in glassy alcohol solution, and only some of these can exhibit substantial excimeric character in their lowest 3IL excited states. A dσ* f π* MMLCT assignment is not preferred due to the lack of evidence for appreciable Pd-Pd bonding. The absence of a low-energy band for 1d and 1f suggests that their geometry disfavor such π-π interactions. Complexes 2e and 5e exhibit dual emissions at λmax ) 480, 523 (τ ) 64 µs), and 633 nm (τ ) 88 µs) and λmax ) 479 (sh), 517 (τ ) 74 µs), and 634 nm (τ ) 16 µs), respectively, in MeOH/EtOH glasses. Like the Pt(II) analogues,1 no apparent photophysical trend arising from the various 4-aryl substituents is observed. Our investigation has shown that the nature of the luminescent excited states of 1e-5e is highly dependent upon the solvent and medium. For example, their emission spectra in frozen acetonitrile at 77 K contain structureless bands at λmax ∼ 600 (28) Non-linear exponential decays for solid-state emission lifetimes were observed.

Figure 9. UV-vis absorption spectra of [M2(L1)2(µ-dppm)]2+ (M ) Pd, Pt) in CH3CN at 298 K.

nm only (assignable to π-π excimeric 3IL transitions), and no high-energy vibronic bands are detected as in MeOH/EtOH glasses. Changes in emissive excited states in different solvents have been reported for binuclear Pt(II) terpyridine complexes.30 The π-stacking conformations leading to an excimeric lowenergy emission are apparently facilitated in rigid, frozen solutions; 1e-5e(ClO4)2 solids do not emit at λmax g 600 nm. This is consistent with the X-ray structural data that revealed non-ideal π-π interactions in the crystal lattices. The structured solid-state emissions (Table 5) are slightly red-shifted from those of MeOH/EtOH glasses, perhaps due to very weak π-π interactions. Comparisons between Pd(II) and Pt(II) Systems. A principal objective of this work is to highlight spectroscopic similarities and differences between the cyclometalated 6phenyl-2,2′-bipyridine Pd(II) and Pt(II) congeners,1,2 in order to shed further light upon the nature of their excited states and intramolecular (d8-d8 and π-π) interactions. The absorption at λ ∼ 390 nm for [Pd(L1)Cl] (1a) in CH2Cl2 is assigned to a MLCT transition. Since the 4d(Pd) orbital exhibits a higher ionization potential than 5d(Pt), a red shift for the corresponding absorption in [Pt(L1)Cl] (λmax ) 430 nm in CH2Cl2) is consistent with this assignment. Shifting of MLCT transitions to lower energies for [M(bph)(bpy)] (H2bph ) biphenyl) from Pd(II) to Pt(II) has been reported.31 A compari(29) Comparable emissions have been observed for Pt(II) terpyridine complexes: (a) Bailey, J. A.; Hill, M. G.; Marsh, R. E.; Miskowski, V. M.; Schaefer, W. P.; Gray, H. B. Inorg. Chem. 1995, 34, 4591. (b) Arena, G.; Calogero, G.; Campagna, S.; Scolaro, L. M.; Ricevuto, V.; Romeo, R. Inorg. Chem. 1998, 37, 2763. (c) Lai, S. W.; Chan, M. C. W.; Cheung, K. K.; Che, C. M. Inorg. Chem. 1999, 38, 4262. (30) Bailey, J. A.; Miskowski, V. M.; Gray, H. B. Inorg. Chem. 1993, 32, 369. (31) Cornioley-Deuschel, C.; von Zelewsky, A. Inorg. Chem. 1987, 26, 3354.

262 Inorganic Chemistry, Vol. 39, No. 2, 2000

Lai et al. Correlation of luminescent properties between the Pd(II) and Pt(II) counterparts is also informative. The 77 K emission of [M2(L1)2(µ-dppm)]2+ in frozen CH3CN occurs at λmax ) 598 and 638 nm for Pd and Pt, respectively (Figure 10). Since a π-π excimeric 3IL transition is invoked for the Pd2 species, the red shift for the Pt2 analogue is indicative of an excitedstate arising from π-π (excimeric 3IL) and metal-metal (previously assigned as dσ* f π*) interactions. In other words, the Pd-Pd interaction in the excited state appears weaker. The 77 K solid-state emission spectra for [M2(L1)2(µ-dppm)](ClO4)2 illustrate a similar trend (Figure 10). A structureless band appears at λmax ) 640 nm for Pt2, while a structured emission is observed at λmax ) 526 and 553 nm for Pd2. The nature of the former is again ascribed to mixed dσ* f π*/excimeric π f π*, while the excited state of the Pd2 species is assigned as 3IL accompanied by weak π-π excimeric character.

Figure 10. Normalized 77 K emission spectra (λex ) 350 nm) of [M2(L1)2(µ-dppm)](ClO4)2 (M ) Pd, Pt) in frozen CH3CN (F) and solid state (S).

son between the UV absorption spectra of [Pd2(L1)2(µ-dppm)]2+ (1e) and its Pt(II) analogue is depicted in Figure 9. The platinum derivative has noticeably higher absorbance at λmax ) 450600 nm, a region where mononuclear counterparts do not absorb, and a dσ* f π* transition was previously assigned. We again conclude that the apparent blue shift in the lowest energy band for 1e signifies exceedingly weak/minimal Pd-Pd interaction in the ground state.

Acknowledgment. We are grateful for financial support from The University of Hong Kong and the Research Grants Council of the Hong Kong SAR, China [HKU 7298/99P]. We thank Dr. V. M. Miskowski for helpful discussions. Supporting Information Available: Listings of crystal data, atomic coordinates, calculated coordinates, anisotropic displacement parameters, and bond lengths and angles for 1d(ClO4), 1e(ClO4)2‚DMF, and 2e(ClO4)2. This material is available free of charge via the Internet at http://pubs.acs.org. IC991089G